CA2023166A1 - Polyarylene ethers - Google Patents
Polyarylene ethersInfo
- Publication number
- CA2023166A1 CA2023166A1 CA 2023166 CA2023166A CA2023166A1 CA 2023166 A1 CA2023166 A1 CA 2023166A1 CA 2023166 CA2023166 CA 2023166 CA 2023166 A CA2023166 A CA 2023166A CA 2023166 A1 CA2023166 A1 CA 2023166A1
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- Prior art keywords
- formula
- mol
- group
- structural unit
- recurring structural
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
K- 17697/+ /CGM349 Novel polyarylene ethers Abstract Polyarylene ethers which contain, based on the total amount of structural units present in the polyether resin, 10-100 mol % of a recurring structural unit of the formula I
(I), 0-50 mol % of a recurring structural unit of the formula II
(II), 0-90 mol % of a recurring structural unit of the formula III
?O-A"-O-A] (III), and 0-50 mol % of a recurring structural unit of the formula IV
?O-A"-C)-A'] - (IV), in which A is a group of the formula Va or Vb (Va) (Vb) in which X is -CO-, a is 0, 1 or 2 and b is 2 or 3, and A' is a group of the formula VIa or VIb (VIa) (VIb) in which Y is -SO- or -SO2-, c is 0 or 1 and d is 2, and A" is a group of the formulae VIIa to VIIe (VIIa), (VIIb), (VIIc), (VIId) or (VIIe), in which Z is a direct bond, -C(CH3)2-, -C(CF3)2-, -S-, SO-, -SO2-, -O- or -CO-.
These industrial materials have very good mechanical and thermal properties.
(I), 0-50 mol % of a recurring structural unit of the formula II
(II), 0-90 mol % of a recurring structural unit of the formula III
?O-A"-O-A] (III), and 0-50 mol % of a recurring structural unit of the formula IV
?O-A"-C)-A'] - (IV), in which A is a group of the formula Va or Vb (Va) (Vb) in which X is -CO-, a is 0, 1 or 2 and b is 2 or 3, and A' is a group of the formula VIa or VIb (VIa) (VIb) in which Y is -SO- or -SO2-, c is 0 or 1 and d is 2, and A" is a group of the formulae VIIa to VIIe (VIIa), (VIIb), (VIIc), (VIId) or (VIIe), in which Z is a direct bond, -C(CH3)2-, -C(CF3)2-, -S-, SO-, -SO2-, -O- or -CO-.
These industrial materials have very good mechanical and thermal properties.
Description
2 ~ 2 3 ~ ~ ~
K-17697/+/CGM 349 Novel polvarvlene ethers The present invention relates to novel polyarylene ethers, to a process for their preparation and to their use as industrial materials.
EP-A-282,096 describes the synthesis of polyarylene ether ketones and sulfones containing l,l'-bis-4-naphthoxy structural units. Aliphatic-aromatic polyethers of diphenols and bis(chloromethyl) derivatives containing units of the 2,2'-dihydroxy-1,1'-dinaphthyl type are furthermore known from M. Tokarzewska, J. Pol.
Sci., Part A-l, Volume 6,777-784, (1968). Polyether ketones containing structural units which are derived from napthalenediols are also described in Japanese Patent Kokai 213,219/86; 11,726/87 and 7~,032/88.
These polymers do not meet in every respect the stringent demands made toclay of a high quality thermoplastic resin. In particular, the glass transition point is unsatisfactoIy, leading to inadequate dimensional stability under heat or to generally inadequate heat stability. The resistance to solvents is furtherrnore insufficient.
The object of the present invention is to provide polyaIylene ethers which are suitable industrial materials having very good mechanical properties and at the same time have a low melting point, a high glass transition temperature, good resistance to solvents and, preferably, partial crystallinity.
Surprisingly, this object is achieved by incorporating structural units which are derived from 2,2'-dihydroxydinaphthyl into the polyarylene ether ketone chain.
The present invention relates to polyarylene ethers which contain, based on the total amount of structural units present in the polyether resin, 10- 100 mol % of a recurring structural unit of the forrnula I
,. . .. .
. . .
~~ 1 (1), ~ ~0--At 0-50 mol % of a recurring structural unit of the forrnula II
~o~3 ~ (l:I), ~ ~0--A~
0-90 mol % of a recurring structural unit of the forrnula III
~0--A"--O--kl-- (III) and 0-50 mol % of a recurring structural unit of the formula IV
~0--A"--O--A' ] (IV), in which A is a group of the formula Va or Vb ~x ~i3X ~ (Va) ~3x ~X~3 (Vb) in which X is -CO-, a is 0, 1 or 2 and b is 2 or 3~ and A' is a group of the formula VIa or VIb ~ Y ~3 y ~ (VIa) :
:, - , , . ~
, ~ , . ~
- : . ~
., , '' ~, ; ':
.
2~
~Y ~ Y~3 (VIb) in which Y is -SO- or -SO2-, c is O or 1 and d is 2, and A" is a group of the formulae VIIa to VIIe ~3 (VIIa), ~ (VIIb3, ~3 Z ~} (VIIC), ~3z ~ Z ~ (VIId) or ~3 z ~3 z ~ z ~} (VIIe)~
in which Z is a direct bond, -C(CH3)2-, -C(CF3)2-, -S-, -SO-, -SO2-, -O- or -CO-.
The polyarylene ethers according to the invention preferably contain 25-100 mol % of a recurring structural unit of the ~ormula I and 0-75 mol % of a recurring structural unit of the formula III and/or 0-50 mol % of a recurring structural unit of the formula IV.
Particularly preferred polyarylene ethers are those in which A is a group of the formula Va, in particular in which a has the value zero.
Polyarylene ethers in which A' is a group of the formula VIa, in particular in which c is zero, are likewise preferred.
The preferred meaning of Y in the formulae VIa and VIb is -SO2-.
Polyarylene ethers in which A" is a group of the forrnulae VIIa and/or VIIc, in which Z is -CO- or a direct bond, are specifically preferred.
Polyarylene ethers in which A in the formulae I and/or III is the group ~ c ~ and A' in the formulae [I and IV is the group ., , ., . -. ~ ~
. .:. . . .
:
~ so2~ are of very particular interest.
The polyarylene ethers according to the invention can be prepared, for example, by subjecting a compound of the formulae VIIIa, VIIIb, lXa and/or IXb Hal ~C~x )~Hal ~VIIIa) Hal ~X ~--~X ~Hal (VIIIb~
Hal ~ Y ~3 Y ~3 Hal (IXa) Hal ~3Y~Y~Hal (lXb~
in which X, Y, a, b, c and d are as defined above and Hal is halogen, in particular fluoro or chloro, to a polycondensation reaction with l,l'-bis-2-naphthol by itself or with a mixture of this compound and a diphenol which is present therein in an amout of up to 90 mol %, of the formula X
HO-A"-OH (X) in which A" is as defined above, in a manner which is known per se, in the presence of alkaline catalysts in a polar aprotic solvent.
Instead of the diphenol of the formula X or the 1,1'-bis-2-naphthol, the corresponding alkali metal phenolate or alkaline earth metal phenolate, for example the potassium or calcium phenolates or corresponding mixtures, can also be employed in a manner which is known per se.
The polycondensation reaction is usually carried out in approximately equimolar ratios of , .:
the compounds VIIIa, VIlIb, l~a, ~b:l,1'-bis-2-naphthol or (1,1'-bis-2-naphthol + X).
Approximately equimolar amounts is understood in this connection as meaning a molar ratio of 0.8:1.2 to 1.2:0.8. A rnolar ratio of 0.95:1.05 to 1.05:0.95 is preferred.
Alkaline catalysts which are used in this process are as a rule alkali metal carhona~es and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate or calcium carbonate, or mixtures thereof, however, other alkaline reagents, such as sodium hydroxide, potassium hydroxide or calcium hydroxide, can also be used.
Examples of polar, aprotic solvents which can be employed in the process for thepreparation of the polyether resins according to the invention are dimethyl sulfoxide, dimethylacetamide, diethylacetamide, tetramethylurea, N-methylcaprolactam, N-methylpyrrolidone and preferably diphenyl sulfone.
The reaction is advantageously carried out at elevated temperatures, preferably up to the reflux temperature of the solvent, that is to say for example up to 350C.
It is often advisable also to use an entraining agent, for example chlorobenzene, xylene or toluene, so that the water formed during the reaction can be removed azeotropically from the reaction mixture.
The compounds of the formulae VIIIa, VIIIb, IXa and IXb are known and are in some cases commercially available. Examples of suitable compounds of these formulae are 4,4'-difluorobenzophenone, 1,3-bis(4-fluorobenzoyl)benzene, 4,4'-dichlorobenzophenone, 4,4'-difluorodiphenyl sulfone or 4,4'-dichlorodiphenyl sulfone.
1,1 '-bis-2-naphthol is known and is commercially available.
The compounds of the formula X are also known compounds and are in rnost cases commercially available. Examples of sui~able dihydric phenols of the forrnula VI are hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl thioether, 2,2-di-(4-hydroxyphenyl)propane and dihydroxynaphthalene.
The polyether resins according to the invention can be employed in the conventional .
7J ~
manner for therrnoplastics and can be processed, for example, to mouldings o} sheets or they can be used as matrix resins, adhesives or coating compounds. The customaryadditives, for example, fillers, pigments, stabilizers or reinforcing agents, such as carbon fibres, boron ~Ibres or glass fibres, can be added before processing of the polyarylene ether which is for example, in the form of a moulding powder, film or melt. Another possible use of the polyarylene ethers according to the invention is the modification of other plastics. These can in principle be thermoplastics or thermosets.
The polyarylene ethers according to the invention are preferably suitable as matrix resins for the production of fibre composite systems, for which utility it is possible to use as reinforcing fibres the fibres conventionally used for reinforcing industrial materials. These fibres can be organic or inorganic ~Ibres, naturally occurring fibres or synthetic fibres, such as aramide fibres, and can be in the form of fibre bundles, oriented or non-oriented ~Ibres or continuous fibres. Glass ~Ibres, asbestos fibres, boron ~Ibres, carbon fibres and metal fibres, for example, are used as the reinforcing fibres.
As the range of utility described above shows, the polyarylene ethers of this invention are widely applicable as industrial materials.
Examples 1-~: A mixture of 28.63 g (0.1000 mol) of 1,1'-bis-2-naphthol,75.68 g of diphenyl sulfone, 15.53 g (0.1124 mol) of potassium carbonate and 57.6 g of xylene is heated at a bath temperature of 200C under nitrogen in a round-bottomed flask with a stirrer, inert gas connection and distillation unit, and a xylene/water mixture is distilled off. Towards the end of the distillation, vacuum (5 mbar) is applied for a short time. 21.40 g (0.0981 mol) of 4,4'-difluorobenzophenone are then added to the reaction rnixture and the temperature is increased to 250C at 2(:/minute and kept for 1 hour. The temperature is subsequently further increased to 320C. Rfter 1.5 hours, 0.49 g (0.0023 mol) of 4,4'-difluorobenzophenone is added, and after a futher 30 minutes another 0.24 g (0.0011 mol) of 4,4'-difluorobenzophenone is added. The temperature is then increased to 350C
and kept for 3.5 hours.
After cooling, the reaction mixture is removed from the flask and pulverised. 2 molar hydrochloric acid is added and the mixture is extracted first with water and then with acetone. The polymer purified in this way is dried in a vacuum drying cabinet at a temperature of up to 240C. A polyether ketone prepared in this manner and containing bisnaphthol units has a glass aansition temperature, determined by DSC, of 225C and a s33 ~
melting point of 310C.
Examples 2-6 shown in the following table are prepared in similar manner.
The polymers are insoluble in acectone and methylene chloride and only sparingly soluble (< 1 %) in N-methylpyrrolidone, but are soluble in concentrated sulfuric acid to give a gel-free solution. The solubility in concentrated sulfuric acid demonstrates the presence of a linear, i.e. non-crosslinked, polyether ketone.
X-ray analysis shows that the polymers contain distinct crystalline fractions. The relative crystallinity of selected examples is deterrnined by radiographic analysis by means of powder diffractometry (Philips PW 1710 powder dfflractometer) with CuKa-irradiation in reflection geometry. The values reported in Table 2 (ra~io of crystalline surface to crystalline and amorphous surface = degree of crystallinity; evaluation in accordance with C.-L. Ong, W.-L. Chung, M.-F. Sheu, J.-H. Lin 33rd Int. SAMPE Symposium 1988, p.1307) indicate clearly that (partially) crystalline polymers are obtained.
A polyether ketone prepared according to Example 2 is pressed in a plate press at 250C
under a force of 3000 N for 10 minutes. A flexible film which can be bent and folded repeatedly without fracture is obtained. The film (thickness: 0.13 mm) has a tensile strength of 60 MPa and an elongation at break of 8 % (according to DIN 53 455).
':
. , ,:
. .
' 7 -~ -~ o o~ ~
o ~ ~ ~o~ ~
- - : -~ ~ 1~' ''' oo o ç~
~` 2 . ; . . . . ~ ... ~,.. .. .
;
.
" . ..
~3~ ~
E 1:1 . .
~ ~ I
o~ _ ~ _ __ :'Y o o CC CJv, C~ go ~
~ O O ~ ~ _. O O ~ C`l !
Table 2: Relative Crystallinity vf the polymers synthesised with 1,1'-bis-2-naphthol . ._ _ Example of Table 1 Degree of crystallinity . _ 1 not determined 2 0.24 3 0.46 4 0.47 0.35 6 0.39 7 not detennined 8 0.17 9 0.37 _ _ _ _ _ :
. .
K-17697/+/CGM 349 Novel polvarvlene ethers The present invention relates to novel polyarylene ethers, to a process for their preparation and to their use as industrial materials.
EP-A-282,096 describes the synthesis of polyarylene ether ketones and sulfones containing l,l'-bis-4-naphthoxy structural units. Aliphatic-aromatic polyethers of diphenols and bis(chloromethyl) derivatives containing units of the 2,2'-dihydroxy-1,1'-dinaphthyl type are furthermore known from M. Tokarzewska, J. Pol.
Sci., Part A-l, Volume 6,777-784, (1968). Polyether ketones containing structural units which are derived from napthalenediols are also described in Japanese Patent Kokai 213,219/86; 11,726/87 and 7~,032/88.
These polymers do not meet in every respect the stringent demands made toclay of a high quality thermoplastic resin. In particular, the glass transition point is unsatisfactoIy, leading to inadequate dimensional stability under heat or to generally inadequate heat stability. The resistance to solvents is furtherrnore insufficient.
The object of the present invention is to provide polyaIylene ethers which are suitable industrial materials having very good mechanical properties and at the same time have a low melting point, a high glass transition temperature, good resistance to solvents and, preferably, partial crystallinity.
Surprisingly, this object is achieved by incorporating structural units which are derived from 2,2'-dihydroxydinaphthyl into the polyarylene ether ketone chain.
The present invention relates to polyarylene ethers which contain, based on the total amount of structural units present in the polyether resin, 10- 100 mol % of a recurring structural unit of the forrnula I
,. . .. .
. . .
~~ 1 (1), ~ ~0--At 0-50 mol % of a recurring structural unit of the forrnula II
~o~3 ~ (l:I), ~ ~0--A~
0-90 mol % of a recurring structural unit of the forrnula III
~0--A"--O--kl-- (III) and 0-50 mol % of a recurring structural unit of the formula IV
~0--A"--O--A' ] (IV), in which A is a group of the formula Va or Vb ~x ~i3X ~ (Va) ~3x ~X~3 (Vb) in which X is -CO-, a is 0, 1 or 2 and b is 2 or 3~ and A' is a group of the formula VIa or VIb ~ Y ~3 y ~ (VIa) :
:, - , , . ~
, ~ , . ~
- : . ~
., , '' ~, ; ':
.
2~
~Y ~ Y~3 (VIb) in which Y is -SO- or -SO2-, c is O or 1 and d is 2, and A" is a group of the formulae VIIa to VIIe ~3 (VIIa), ~ (VIIb3, ~3 Z ~} (VIIC), ~3z ~ Z ~ (VIId) or ~3 z ~3 z ~ z ~} (VIIe)~
in which Z is a direct bond, -C(CH3)2-, -C(CF3)2-, -S-, -SO-, -SO2-, -O- or -CO-.
The polyarylene ethers according to the invention preferably contain 25-100 mol % of a recurring structural unit of the ~ormula I and 0-75 mol % of a recurring structural unit of the formula III and/or 0-50 mol % of a recurring structural unit of the formula IV.
Particularly preferred polyarylene ethers are those in which A is a group of the formula Va, in particular in which a has the value zero.
Polyarylene ethers in which A' is a group of the formula VIa, in particular in which c is zero, are likewise preferred.
The preferred meaning of Y in the formulae VIa and VIb is -SO2-.
Polyarylene ethers in which A" is a group of the forrnulae VIIa and/or VIIc, in which Z is -CO- or a direct bond, are specifically preferred.
Polyarylene ethers in which A in the formulae I and/or III is the group ~ c ~ and A' in the formulae [I and IV is the group ., , ., . -. ~ ~
. .:. . . .
:
~ so2~ are of very particular interest.
The polyarylene ethers according to the invention can be prepared, for example, by subjecting a compound of the formulae VIIIa, VIIIb, lXa and/or IXb Hal ~C~x )~Hal ~VIIIa) Hal ~X ~--~X ~Hal (VIIIb~
Hal ~ Y ~3 Y ~3 Hal (IXa) Hal ~3Y~Y~Hal (lXb~
in which X, Y, a, b, c and d are as defined above and Hal is halogen, in particular fluoro or chloro, to a polycondensation reaction with l,l'-bis-2-naphthol by itself or with a mixture of this compound and a diphenol which is present therein in an amout of up to 90 mol %, of the formula X
HO-A"-OH (X) in which A" is as defined above, in a manner which is known per se, in the presence of alkaline catalysts in a polar aprotic solvent.
Instead of the diphenol of the formula X or the 1,1'-bis-2-naphthol, the corresponding alkali metal phenolate or alkaline earth metal phenolate, for example the potassium or calcium phenolates or corresponding mixtures, can also be employed in a manner which is known per se.
The polycondensation reaction is usually carried out in approximately equimolar ratios of , .:
the compounds VIIIa, VIlIb, l~a, ~b:l,1'-bis-2-naphthol or (1,1'-bis-2-naphthol + X).
Approximately equimolar amounts is understood in this connection as meaning a molar ratio of 0.8:1.2 to 1.2:0.8. A rnolar ratio of 0.95:1.05 to 1.05:0.95 is preferred.
Alkaline catalysts which are used in this process are as a rule alkali metal carhona~es and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate or calcium carbonate, or mixtures thereof, however, other alkaline reagents, such as sodium hydroxide, potassium hydroxide or calcium hydroxide, can also be used.
Examples of polar, aprotic solvents which can be employed in the process for thepreparation of the polyether resins according to the invention are dimethyl sulfoxide, dimethylacetamide, diethylacetamide, tetramethylurea, N-methylcaprolactam, N-methylpyrrolidone and preferably diphenyl sulfone.
The reaction is advantageously carried out at elevated temperatures, preferably up to the reflux temperature of the solvent, that is to say for example up to 350C.
It is often advisable also to use an entraining agent, for example chlorobenzene, xylene or toluene, so that the water formed during the reaction can be removed azeotropically from the reaction mixture.
The compounds of the formulae VIIIa, VIIIb, IXa and IXb are known and are in some cases commercially available. Examples of suitable compounds of these formulae are 4,4'-difluorobenzophenone, 1,3-bis(4-fluorobenzoyl)benzene, 4,4'-dichlorobenzophenone, 4,4'-difluorodiphenyl sulfone or 4,4'-dichlorodiphenyl sulfone.
1,1 '-bis-2-naphthol is known and is commercially available.
The compounds of the formula X are also known compounds and are in rnost cases commercially available. Examples of sui~able dihydric phenols of the forrnula VI are hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl thioether, 2,2-di-(4-hydroxyphenyl)propane and dihydroxynaphthalene.
The polyether resins according to the invention can be employed in the conventional .
7J ~
manner for therrnoplastics and can be processed, for example, to mouldings o} sheets or they can be used as matrix resins, adhesives or coating compounds. The customaryadditives, for example, fillers, pigments, stabilizers or reinforcing agents, such as carbon fibres, boron ~Ibres or glass fibres, can be added before processing of the polyarylene ether which is for example, in the form of a moulding powder, film or melt. Another possible use of the polyarylene ethers according to the invention is the modification of other plastics. These can in principle be thermoplastics or thermosets.
The polyarylene ethers according to the invention are preferably suitable as matrix resins for the production of fibre composite systems, for which utility it is possible to use as reinforcing fibres the fibres conventionally used for reinforcing industrial materials. These fibres can be organic or inorganic ~Ibres, naturally occurring fibres or synthetic fibres, such as aramide fibres, and can be in the form of fibre bundles, oriented or non-oriented ~Ibres or continuous fibres. Glass ~Ibres, asbestos fibres, boron ~Ibres, carbon fibres and metal fibres, for example, are used as the reinforcing fibres.
As the range of utility described above shows, the polyarylene ethers of this invention are widely applicable as industrial materials.
Examples 1-~: A mixture of 28.63 g (0.1000 mol) of 1,1'-bis-2-naphthol,75.68 g of diphenyl sulfone, 15.53 g (0.1124 mol) of potassium carbonate and 57.6 g of xylene is heated at a bath temperature of 200C under nitrogen in a round-bottomed flask with a stirrer, inert gas connection and distillation unit, and a xylene/water mixture is distilled off. Towards the end of the distillation, vacuum (5 mbar) is applied for a short time. 21.40 g (0.0981 mol) of 4,4'-difluorobenzophenone are then added to the reaction rnixture and the temperature is increased to 250C at 2(:/minute and kept for 1 hour. The temperature is subsequently further increased to 320C. Rfter 1.5 hours, 0.49 g (0.0023 mol) of 4,4'-difluorobenzophenone is added, and after a futher 30 minutes another 0.24 g (0.0011 mol) of 4,4'-difluorobenzophenone is added. The temperature is then increased to 350C
and kept for 3.5 hours.
After cooling, the reaction mixture is removed from the flask and pulverised. 2 molar hydrochloric acid is added and the mixture is extracted first with water and then with acetone. The polymer purified in this way is dried in a vacuum drying cabinet at a temperature of up to 240C. A polyether ketone prepared in this manner and containing bisnaphthol units has a glass aansition temperature, determined by DSC, of 225C and a s33 ~
melting point of 310C.
Examples 2-6 shown in the following table are prepared in similar manner.
The polymers are insoluble in acectone and methylene chloride and only sparingly soluble (< 1 %) in N-methylpyrrolidone, but are soluble in concentrated sulfuric acid to give a gel-free solution. The solubility in concentrated sulfuric acid demonstrates the presence of a linear, i.e. non-crosslinked, polyether ketone.
X-ray analysis shows that the polymers contain distinct crystalline fractions. The relative crystallinity of selected examples is deterrnined by radiographic analysis by means of powder diffractometry (Philips PW 1710 powder dfflractometer) with CuKa-irradiation in reflection geometry. The values reported in Table 2 (ra~io of crystalline surface to crystalline and amorphous surface = degree of crystallinity; evaluation in accordance with C.-L. Ong, W.-L. Chung, M.-F. Sheu, J.-H. Lin 33rd Int. SAMPE Symposium 1988, p.1307) indicate clearly that (partially) crystalline polymers are obtained.
A polyether ketone prepared according to Example 2 is pressed in a plate press at 250C
under a force of 3000 N for 10 minutes. A flexible film which can be bent and folded repeatedly without fracture is obtained. The film (thickness: 0.13 mm) has a tensile strength of 60 MPa and an elongation at break of 8 % (according to DIN 53 455).
':
. , ,:
. .
' 7 -~ -~ o o~ ~
o ~ ~ ~o~ ~
- - : -~ ~ 1~' ''' oo o ç~
~` 2 . ; . . . . ~ ... ~,.. .. .
;
.
" . ..
~3~ ~
E 1:1 . .
~ ~ I
o~ _ ~ _ __ :'Y o o CC CJv, C~ go ~
~ O O ~ ~ _. O O ~ C`l !
Table 2: Relative Crystallinity vf the polymers synthesised with 1,1'-bis-2-naphthol . ._ _ Example of Table 1 Degree of crystallinity . _ 1 not determined 2 0.24 3 0.46 4 0.47 0.35 6 0.39 7 not detennined 8 0.17 9 0.37 _ _ _ _ _ :
. .
Claims (9)
1. A polyarylene ether which contains, based on the total amount of structural units present in the polyether resin, 10-100 mol % of a recurring structural unit of the formula I
(I), 0-50 mol % of a recurring structural unit of the formula II
(II), 0-90 mol % of a recurring structural unit of the formula III
? O-A"-O-A? (III) and 0-50 mol % of a recurring structural unit of the formula IV
? O-A"-O-A'? (IV), in which A is a group of the formula Va or Vb (Va) (Vb) in which X is -CO-, a is 0, 1 or 2 and b is 2 or 3, and A' is a group of the formula VIa or VIb (VIa) (VIb) in which Y is -SO- or -SO2-, c is 0 or 1 and d is 2, and A" is a group of the formulae VIIa to VIIe (VIIa), (VIIb), (VIIc), (VIId) or (VIIe), in which Z is a direct bond, -C(CH3)2-, -C(CF3)2-, -S-, -SO-, -SO2-, -O- or -CO-.
(I), 0-50 mol % of a recurring structural unit of the formula II
(II), 0-90 mol % of a recurring structural unit of the formula III
? O-A"-O-A? (III) and 0-50 mol % of a recurring structural unit of the formula IV
? O-A"-O-A'? (IV), in which A is a group of the formula Va or Vb (Va) (Vb) in which X is -CO-, a is 0, 1 or 2 and b is 2 or 3, and A' is a group of the formula VIa or VIb (VIa) (VIb) in which Y is -SO- or -SO2-, c is 0 or 1 and d is 2, and A" is a group of the formulae VIIa to VIIe (VIIa), (VIIb), (VIIc), (VIId) or (VIIe), in which Z is a direct bond, -C(CH3)2-, -C(CF3)2-, -S-, -SO-, -SO2-, -O- or -CO-.
2. A polyarylene ether according to claim 1, which contains 25-100 mol % of a recurring structural unit of the formula I and 0-75 mol % of a recurring structural unit of the formula III and/or 0-50 mol % of a recurring structural unit of the formula IV.
3. A polyarylene ether according to claim 1, in which A is a group of the formula Va.
4. A polyarylene ether according to claim 1, in which A' is a group of the formula VIa.
5. A polyarylene ether according to claim 4, in which Y is -SO2-.
6. A polyarylene ether according to claim 1, in which A" in the formulae III and/or IV is a group of the formulae VIIa andlor VIlc, in which Z is -CO- or a direct bond.
7. A polyarylene ether according to claim 1, in which A is the group and A' is the group .
8. A process for a preparation of a polyarylene ether according to claim 1, which comprises subjecting a compound of the folmulae VIIIa, VIIlb, IXa and/or IXb (VIIIa) (VIIIb) (IXa) (IXb) in which X, Y, a, b, c and d are as defined above and Hal is halogen, in particular fluoro or chloro, to a polycondensation reaction with 1,1'-bis-2-naphthol by itself or with a mixture of said compound and a diphenol which is present therein in an amout of up to 90 mol %, of the formula X
HO-A"-OH (X) in which A" is as defined above, in a manner which is known per se, in the presence of alkaline catalysts in a polar aprotic solvent.
HO-A"-OH (X) in which A" is as defined above, in a manner which is known per se, in the presence of alkaline catalysts in a polar aprotic solvent.
9. A process according to clairn 8, wherein the corresponding alkali metal phenolate or alkaline earth metal phenolate is employed instead of the diphenol of the formula X or the 1, 1'-bis-2-naphthol.
FO 7.3/MJ/cc*
FO 7.3/MJ/cc*
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH297489 | 1989-08-15 | ||
| CH2974/89-0 | 1989-08-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2023166A1 true CA2023166A1 (en) | 1991-02-16 |
Family
ID=4245821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2023166 Abandoned CA2023166A1 (en) | 1989-08-15 | 1990-08-13 | Polyarylene ethers |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0413662A3 (en) |
| JP (1) | JPH0388829A (en) |
| CA (1) | CA2023166A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7176278B2 (en) | 2001-08-30 | 2007-02-13 | Biorexis Technology, Inc. | Modified transferrin fusion proteins |
| WO2008012629A2 (en) | 2006-07-24 | 2008-01-31 | Biorexis Pharmaceutical Corporation | Exendin fusion proteins |
| GB0625487D0 (en) * | 2006-12-21 | 2007-01-31 | Victrex Mfg Ltd | Composite material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4806617A (en) * | 1987-03-13 | 1989-02-21 | The B.F. Goodrich Company | Poly(dinaphthyl arylene ether) and preparation thereof |
-
1990
- 1990-08-07 EP EP19900810597 patent/EP0413662A3/en not_active Withdrawn
- 1990-08-13 CA CA 2023166 patent/CA2023166A1/en not_active Abandoned
- 1990-08-15 JP JP21567590A patent/JPH0388829A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0388829A (en) | 1991-04-15 |
| EP0413662A3 (en) | 1991-10-23 |
| EP0413662A2 (en) | 1991-02-20 |
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